Vat dyestuffs of the anthraquinone series



Patented July 2, 1948 UNITED STATES PATENT OFFICE VAT D'YESTUFFS on THE ANTHRAQUINON seams Otto Schlichtin g,

Germany, assignor Ludwigshafen-on-the-Rhine, to General Aniline &'.Film

Corporation, a corporation of Delaware N9 w ng. Application December 16, 1938,

Serial O- 246,126. In Germany July-8, 193

, 8 Claims (01. 260-303) The present invention relates to vat dyestuffs of the anthraquinone series. This application is a continuation-in-part of my application Ser. No. 152,375 filed July '7, 1937.

I have found that compounds of the anthraquinone series corresponding to the general formula (in which A is the radical of an anthraquinone, ,X is oxygen, sulphur or an imino group, R is a radical of the benzene series and Z is a radical of the anthraquinone series) are valuable Vat dyestuffs.

The said compounds may be obtained by various methods:

(A) For example, they maybe prepared by causing anthraquinoneazoles of the structure X A CR-W wherein A, X and R have the meanings mentioned above and W stands for a carboxylic acid, carboxylic acid amide, carboxylic acid anhydride or carboxylic acid halide group to react with amino compounds of the anthraquinone series. The anthraquinone azoles may contain the azole ring at any two adjacent positions of the anthraquinone A which latter may contain any desired atoms or groups. The amino compounds of the anthraquinone series employed for this process may contain any atoms or groups, for instance halogen atoms or acylamino groups and they may be derived from anthraquinone, anthrapyrimi: dine, anthanthrone, p'yranthrone, dibenzpyrenequinone, benzanthrone, benzanthraquinone, azannection there may be mentioned for example aminoanthraquinones containing halogen or a hydro'xy, mercapto or amino group in ortho position to the amino group. The preparation of thiazoles may also be carried out by efiecting" this reaction with aminoanthraquinone while simultaneously orsubsequently adding sulphur or.

sulphurizing agents.

(C) Finally the said compounds may be prepared by causing compounds of the composition V-R-V in which RandV have the meanings mentioned in the second and the foregoing para: graphs respectively, to react simultaneously or subsequently with an aminoanthraquinone which allows of the attachment of an azole ring and with amino compound of the anthraquinone series. As starting material oithe composition VR,-V may be mentioned by way of example the halides; of the terephthalic acid, the isophthalic acid, the'diphenyl-4,4-dicarboxylic acid and the teriohenyl-para-para-dicarboxylic acid.

The new vat dyestufis thus obtainable have various shades of color depending on the initial materials. The yields are usually very good and in most cases correspond to ,the theoretical yields.

If necessary the dyestuffs may be. purified by usual methods, as forexample'by crystallisation I or by treatment with oxidising agents. They are.

distinguished by good fastness to light, chlorine and kier boiling.

The following examples will further illustrate how the said invention may be carried out in practice but the invention is not restricted to these examples. The parts are by weight.

Example 1 A mixture of 13 parts of l-mercapto-Z-aminoanthraquinone, 15 parts of 4,4'-diphenyldicarboxylic acid chloride, 1 part of para-toluenesulphonic acid and 150, parts of nitrobenzene is heated while stirring at from l50-l60 G. for 1 hour, 150 parts of nitrobenzene and 12 parts of I-aminoanthraquinone are then added and the whole is boiled for about 2 hours. After cooling to about 100 C. the deposited dyestuff is filtered off by suction, washed with nitrobenzene and methanol and dried. The dyestufi H o S G C 0-1 1 0 II y l l 0 V 0 thus obtained is a yellow crystal powder which dissolves in concentrated sulphuric acid giving a yellow coloration, and which dyes from a redviolet vat vegetable fibres greenish yellow shades f good fastness properties.

Similar dyestufis are obtained when the l-aminoanthraquinone is replaced by l-amino-E-benzoylaminoanthraquinone or by 2 or 4- or 5- or 8-amino-1.9-anthrapyrimidine.

Example 2 A mixture of 17 parts of 1-amino-5-benzoylaminoanthraquinone, 15 parts of 4,4'-diphenyldicarboxylic acid chloride and 200 parts of nitrobenzene is heated while stirring at about 150 C. until the chloride of the formula has been formed. Then a mixture of 13 parts of 1-mercapto-2-aminoanthraquinone, 1 part of para-toluenesulphonic acid and 200 parts of nitrobenzene is added and the whole is heated at about 200 C. until initial material is no longer detectable. After cooling to about C. the deposited dyestuff is filtered off by suction, washed with nitrobenzene and methanol and dried. The dyestuff thus obtained in a good yield is a yellow crystal powder which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes from a red-violet vat cotton yellow shades of good fastness properties.

Similar dyestuffs are obtained when instead of l-amino-5-benzoylaminoanthraquinone, l amino-5-chloranthraquinone or l-aminol-methoxyanthraquinone or 1-amino-5-methoxyanthraquinone is used.

Example 3 A mixture of 24 parts of 2-amino-3ehydroxyanthraquinone, 1 part of para-toluenesulphonic acid, 600 parts of nitrobenzene and 47 parts of the chloride of the formula (obtainable by condensation of 1 molecularvproportion of l-amino-anthraquinone with l molecular proportion of 4,4-diphenyldicarboxylio acid chloride in ortho-dichlorbenzene) is boiled while stirring for 2 hours. The deposited dyestuff is worked up in the usual manner. The new dyestuff thus obtained as a yellow crystal powder has the formula and dissolves in concentrated sulphuric acid giving a yellow coloration and dyes from a red vat cotton yellow shades of good fastness properties.

Corresponding dyestuffs are obtained if l-amino-2-hydroxyanthraquinone or l-mercapto 2- aminoanthraduinone be employed instead of 2-amino-3-hydroxyanthraquinone.

Example 4 O O ITT CO-CsHs is obtained as an orange colored crystal powder which dissolves in concentrated sulphuric acid giving a yellow-red coloration and which dyes from a red vat vegetable fibres yellow shades of good fastness properties.

If instead of 1amino-5-benzoylaminoanthra quinone, the l-aminoanthraquinone is used a dyestufl is obtained which dyes cotton greenish yellow shades. Furthermore good dyestufls are obtained if 2- [4-aminophenyl-l [anthraquinono-l(N).2:4.5-oxazolel or Z-EIA-diaminoanthraquinonyl-2l-[anthraquinono 2'.3 24.5 oxazole] or 4 amino 5' chloranthraquinonel (N).2.2'(N)l-benzacridone be used instead of l-amino-5benzoylaminoanthraquinone.

Example 5 A mixture of 26 parts of 1-mercapto-2-aminoanthraquinone, 25 parts of terephthalic acid chloride and 250 parts of nitrobenzene is heated.

while stirring at 180 C. for an hour. After add ing parts of nitrobenzene and 23 parts of l-aminoanthraquinone the whole is boiled for an hour. After working up in the usual manner the dyestufi' O a, p is obtained. By-products may be removed by treatment with hot trichlorbenzene or nitrobene zone or With an alkaline sodium hypochlorite f. g i

Example 6 A mixture of 25 parts of 1-amino-2-hydroxyanthraquino-ne, 25 parts of terephthalic acid chloride and 250 parts of nitrobenzene is heated while stirring at 180 C.-for 2 hours. After adding 150 parts of nitrobenzene and 35 parts of 1 -amino-5-benzoylaminoanthraquinone the whole is boiled for 1 hour and worked up in the usual manner. The dyestuff thus obtained -cooem H dissolves in concentrated sulphuric acid giving a yellow coloration and dyes cotton yellow shades from a red vat;

Similar dyestufis are obtained when 2-amino- S-hydroxyanthraquinone or 1.2-diaminoanthraquinone is used instead of l-amino-Z-hydroxyanthraquinone.

Example 7 A mixture of 24 parts of 1.2-diaminoanthraquinone, 1 part of para-toluenesulphonic acid, 500 parts of nitrobenzene and 40 parts of the following chloride COOI (obtainable by heating 1 molecular proportion of l-aminoanthraquinone with 1 molecular proportion of isophthalic acid chloride in orthodichlorbenzene) is heated while stirring at 200 C. for about 2 hours. After working up in the usual manner the dyestufi NH CO-NH I0 is obtained as a yellow crystal powder which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes from a red vat cotton greenish yellow shades of good fastness properties.

v In a manner a reddish yellow dyestufi is obtained when the following chloride COG] CuH5C oN1!i o is used instead of the above mentioned chloride.

Example 8 A mixture of 26 parts of l-mercapto-Z-aminoanthraquinone, 23 parts of l-aminoanthraquinone, 25 parts of isophthalic acid chloride, 1 part of para-toluenesulphonic acid is heated while stirring at 150 C. for an hour and then boiled for about 2 hours. After cooling to about 100 C. the deposited crystal pulp is filtered off by suction, washed with nitrobenzene and methanol and dried. The resulting dyestufi is a yellow powder and probably has the following composition It dissolves in concentrated sulphuric acid giving a yellow coloration and it dyes cotton yellow shades from a red-violet vat.

If para-para-terphenyldicarboxylic acid chloride instead of isophthalic acid chloride is used there is obtained a similar yellow dyestuff.

Example 9 A mixture of 24 parts of l-amino-2-hydroxyanthraquinone, 22.5 parts of l-aminoanthraquinone, 21 parts of isophthalyl chloride, 2 parts of para-toluencsulphonic acid and 400 parts of nitrobenzene .is heated to boiling for about 2 hours while stirring. The whole is allowed to cool to from about to 70 C. and the yellow crystal pulp is filtered off by suction and washed with nitrobenzene and methanol. I The result ing dyestufi is a yellow powder and probably has the following composition:

It dyes cotton greenish yellow shades from a violet-tinged red vat. Y I

It may also be prepared by first causing 1 molecular proportion of 1-amino-2-hydroxyanthraquinone to react with 1 molecular proportion of isophthalyl chloride so that one acid chloride group of the isophthalyl chloride is still free, and then treating this acid chloride with l-aminoanthraquinone, or by causing the C- phenylanthraquinone-l (N) .2 oxazo-le-3'-carboxylic acid (obtainable from 6.3-methy1phenylanthraquinone-l(N).2-oxazole by oxidation with sodium bichromate and sulphuric acid) to react in the form of its acid chloride with l-aminoanthraquinone.

What I claim is:

l. A vat dyestuff of the anthraqulnone series corresponding to the general formula wherein A stands for the radical of an anthraquinone, X for a member selected from the class consisting of H -o-, -sand N R for a cyclic radical selected from the class consisting of benzene, diphenyl and terphenyl, and Z for a radical of the anthraquinone series.

2. A vat dyestuff of the anthraquinone series corresponding to the general formula H A CRCO-N-Z wherein A stands for the radical of the anthraquinone, X for a member selected from the class consisting of wherein A stands for the radical of the anthraquinone, X for a member selected from the class consisting of O, S and and Z for a radical of the anthraquinone series.

4. A vat dyestuff of the anthraquinone series corresponding to the general formula wherein A stands for the radical of the anthraquinone, X for a member selected from the class consisting of H O, S- and N- and Z for a radical of the anthraquinone series.

5. A vat dyestufi of the anthraquinone series corresponding to the general formula wherein A stands for the radical of the anthraquinone, X for a member selected from the class consisting of H 0, -sand -N- and Z for an anthraquinone radical combined in the alpha-position to 6. The vat dyestuff of the formula which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes vegetable fibres greenish yellow shades from a redviolet vat.

7. The vat dyestufi of the formula which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes vegetable fibres yellow shades from a red-violet vat.

8. The vat dyestuff of the formula II N.

which dissolves in concentrated sulphuric acid giving a yellow coloration and which dyes vegetable fibres yellow shades from a red-violet vat. OTTO SCI-ILICHTING. 

